Method for producing stable fluorine-containing water-dispersible latexes

ABSTRACT

A process is disclosed for making stable colloidal dispersions (latexes) that form polymeric films containing fluoro-monomers such as heptadecafluorodecyl methacrylate (FMA), heptadecafluorodecyl acrylate (FA), heptadecafluoro-1-decene (FD), heptafluorobutyl acrylate (FBA), and heptafluorobutyl methacrylate (FBMA). The process involves use of a surfactant system containing a fluorocarbon-containing phosphoric acid ester salt such as phosphoric acid bis(tridecafluorooctyl) ester ammonium salt and an anionic alkyl sulfate such as sodium dodecyl sulfate. The combination of polymerization conditions and surfactant system facilitates a suitable environment for the aqueous copolymerization of the fluoro-monomer with one or more co-monomers in the acrylate and/or methacrylate families, such as n-butyl acrylate and methyl methacrylate.

This application claims the benefit of Provisional Applications Ser. No.60/665,335 filed Mar. 24, 2005 and Ser. No. 60/711,437 filed Aug. 24,2005.

The United States government has a paid-up license in this invention andthe right in limited circumstances to require the patent owner tolicense others on reasonable terms as provided for the terms of contractnumbers DMR0213883 and DMR EEC 0002775 awarded by the National ScienceFoundation.

BACKGROUND OF THE INVENTION

The incorporation of fluorine-containing monomers into polymeric systemshas been of considerable interest for a number of years due to the factthat their presence may introduce a number of unique physical andchemical properties. While such properties as thermal stability andchemical resistance are expected to be enhanced, decreases in surfacetension and friction are consequences resulting from the presence offluorine-containing species. However, exceptionally reduced surfacetension and solubility in aqueous environments makes synthetic effortsquite challenging.

Although there are obvious advantages and benefits in generatingfluorine-containing polymers via emulsion polymerization, theirincorporation into colloidal particles is not straightforward. Theprimary reason is the immiscibility between hydrophobic C-F entities andthe continuous aqueous phase resulting from large surface tensiondifferences. Due to the fact that emulsion polymerization relies on thediffusion of monomers from monomer droplets through the aqueous phase tomicelles for polymerization to occur, this process is severely limited,thus colloidal particles with only minor concentration levels offluorine-containing species have been generated. Several syntheticattempts have been made to produce fluorine-containing colloidaldispersions in which organic solvents, high shear rates, homogenizers,fluorinated surfactants, and sonication techniques were utilized tofacilitate monomer diffusion through an aqueous phase. Although theseapproaches have been somewhat successful, their preparation can be quiteelaborate even with relatively low fluorine-content, thus inhibitingdesirable film properties. Another approach to increase thefluorine-content of colloidal dispersions was to incorporate fluorine-containing acrylates into colloidal particles. The presence of thependant —CF₃ end groups on the perfluoroalkyl side chains appear togenerate even lower surface tensions than correspondingpolytetrafluoroethylene (—CF₂—) polymers and their derivatives.

SUMMARY OF THE INVENTION

The present invention provides a process for making stable colloidaldispersions (latexes) that form polymeric films containingfluoro-monomers such as heptadecafluorodecyl methacrylate (FMA),heptadecafluorodecyl acrylate (FA), heptadecafluoro-1-decene (FD),heptafluorobutyl acrylate (FBA), and heptafluorobutyl methacrylate(FBMA). The process involves use of a surfactant system containing afluorocarbon-containing surfactant, preferably a fluorocarbon containingphosphoric acid ester salt such as phosphoric acidbis(tridecafluorooctyl) ester ammonium salt (FSP). The surfactant systemdesirably includes an anionic alkyl sulfate surfactant such as sodiumdodecyl sulfate (SDS). The combination of polymerization conditions andsurfactant system facilitates a suitable environment for the aqueouscopolymerization of the fluoro-monomer with one or more co-monomers inthe acrylate and/or methacrylate families, such as n-butyl acrylate andmethyl methacrylate. The resulting colloidal particle morphologiesconsisted of two distinct phases, where MMA and nBA randomly polymerizedforming spherical particles after which FMA polymerized onto theexterior of p-MMA/nBA colloidal particles generating non-sphericalmorphologies. The unique aspect of this approach was that the synthesisof colloidal particles containing fluoropolymers was accomplished usinga classical emulsion polymerization approach without complex reactionsetups, co-solvents, or other accessories.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A, B and C are transmission electron micrographs of (A) MMA/nBA,(B) MMA/nBA/FMA(8.5% w/w of FMA), and (C) MMA/nBA/FMA (15% w/w of FMA)particles.

FIG. 2. Kinetic coefficient of friction plotted as a function ofcolloidal composition. The same γ-axis is also used to plot contactangle measurements (values should be multiplied by 1000).

FIG. 3. AFM phase images of copolymer films: A—MMA/nBA, B—MMA/nBA/FMA,C—MMA/nBA/FA, D—MMA/nBA/FD, E—MMA/nBA/FBMA, and F—MMA/nBA/FBA. Scan boxfor each image is 5 μm×5 μm.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The synthesis of F-containing colloidal dispersions may be troublesomebecause water-monomer miscibility in the presence of afluorine-containing monomer is low due to the hydrophobic nature of thefluorinated species. In order to overcome these difficulties a simplesynthetic procedure was developed in a first embodiment of the inventionthat allows the incorporation of fluorine-containing monomers intoMMA/nBA copolymer particles by utilizing a fluorocarbon containingsurfactant, such as SDS/FSP surfactant mixture. This approachfacilitates the reduction of the surface tension of the aqueous phase,thus increasing the ability of the fluorine -containing monomer todiffuse into micelles. For example, the addition of 0.98% SDS (w/waqueous solution) decreases the surface tension of the aqueous phasefrom 73 mN/m to 38 mN/m, and polymerization reactions conducted underthese conditions in the presence of FMA generate colloidal dispersionscontaining a large degree of coagulum. On the other hand, the additionof SDS along with FSP (0.98% and 0.62% w/w aqueous solution,respectively) further reduces the surface tension of the aqueous phaseto 19 mN/m. These conditions, as described in the Examples, provide asuitable environment for the synthesis of MMA/nBA/FMA copolymerparticles containing up to 8.5% (w/w) FMA monomer.

Short and long chain fluorinated acrylates can be used as thefluorine-containing monomers, including without limitation:heptadecafluorodecyl methacrylate (FMA), heptadecafluorodecyl acrylate(FA), heptadecafluoro-1-decene (FD), heptafluorobutyl acrylate (FBA),and heptafluorobutyl methacrylate (FBMA). Almost any film formingmonomers can be used if one wants to make films. While the preferredfluorocarbon containing surfactant is a phosphoric acid esterfluorocarbon, any fluorinated surfactant is useful. In particular, theZONYL brand fluorosurfactants sold by DuPont are especially preferred.

In a second embodiment of the invention, p-methyl methacrylate/n-butylacrylate/heptadecafluorodecyl methacrylate (p-MMA/nBA/FMA) colloidaldispersions containing up to 15% w/w of FMA were produced by utilizationof biologically active phospholipids (PLs) in combination with ionicsurfactants. The surfactants were1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC), sodium dodecyl sulfate(SDS) and phosphoric acid bis (tridecafluoro-octyl) ester ammonium salt(FSP), these surfactants function as transfer and dispersing agents,facilitate a suitable environment for polymerization of p-MMA/nBA/FMAcolloidal dispersions that exhibit non-spherical particle morphologies.Such non-spherical particles upon coalescence form phase-separated filmswith unique surface properties.

EXAMPLE 1

T Methyl methacrylate (MMA), n-butyl acrylate (nBA),heptadecafluorodecyl methacrylate (FMA), potassium persulfate (KPS), andsodium dodecyl sulfate (SDS) were all purchased from Aldrich ChemicalCo. Phosphoric acid bis(tridecafluoro-octyl) ester ammonium salt (FSP),was received from DuPont. The structures of SDS and FSP surfactants areshown below.

All colloidal dispersions were synthesized under monomer-starvedconditions using a semi-continuous polymerization process in which allmonomer and surfactants were dissolved in water and stirred under highagitation to produce a semi-stable pre-emulsion. 10% (w/w) of thepre-emulsion and 18% (w/w) of the initiator solution potassiumpersulfate were injected into the reaction kettle which contained 100 gof water. This process facilitates the seeding of the emulsionpolymerization. The mixture was then stirred for 30 minutes to allow forinitiation reactions to occur. The remaining pre-emulsion was fedcontinuously over 3.5 hr and the initiator solution was fed over 4 hr.Upon the completion of the initiator feed, polymerization was allowed tocontinue for an additional 5 hr. Polymerization reaction was carried outin a 1 L reaction kettle equipped with a reflux condenser at 79° C. in aN₂ atmosphere under continuous agitation (300 rpm) using a CaframoBDC3030 digital stirrer. Particle size measurements were obtained usinga Microtrac UPA 250, and Table 1 lists the resulting particle sizes, %solids (w/w), and concentration levels of individual components. TABLE 1Colloidal Dispersion Compositions Specimens A B C D E FMA (w/w %) 0 01.22 1.94 3.27 MMA (w/w %) 18.9 18.9 18.3 18.8 18.1 nBA (w/w %) 18.318.3 17.7 18.1 17.4 SDS (w/w %) 0.61 0.61 0.61 0.60 0.60 FSP (w/w %) 00.97 0.97 0.95 0.95 KPS (w/w %) 0.23 0.23 0.23 0.22 0.22 DDI (w/w %)61.96 60.96 60.97 59.39 59.46 Particle Size (nm) 91 94 97 102 104 %Solids 45 42 41 43 42

As listed, specimen A represents MMA/nBA colloidal dispersions preparedin the presence of SDS, specimen B is MMA/nBA prepared using SDS/FSPsurfactants. The same SDS/FSP mixture was used to prepare specimens C,D, and E which contain 3.3, 5, and 8.5% w/w FMA copolymer content,respectively. Such prepared colloidal dispersions were cast on apolyvinylchloride (PVC) substrate and allowed to coalescence at 50%relative humidity (RH) for 3 days at 23° C. to form approximately 20 μmthick films. Film thickness was determined by using a Pro Max caliper.

Polarized attenuated total reflectance Fourier transform infrared (ATRFTIR) spectra were collected using a Bio-Rad FTS-6000 FTIR single-beamspectrometer set at a 4 cm⁻¹ resolution which was equipped with a ZnSepolarizer. A 45° face angle Ge crystal with 50×20×3 mm was used. The useof a ZnSe polarizer facilitates orientation studies by utilizing TE(transverse electric) and TM (transverse magnetic) modes of polarized IRlight. Each spectrum represents 100 co-added scans ratioed against thesame number of reference scans collected using an empty ATR cell. Allspectra were corrected for spectral distortions and optical effectsusing Q-ATR software.

Transmission electron micrographs (TEM) were acquired on a Zeiss EM 109Tmicroscope using an accelerating voltage of 80 kV. Samples of colloidaldispersion used for TEM analysis were prepared by making a 1:10,000dilution in deionized water followed by casting onto Formvar coatedcopper grids (Ted Pella, Inc.). Particle size and particle sizedistribution measurements were performed using a Microtrac UPA 250.

Surface tension measurements of polymeric films and solutions wereconducted by using a FTA200 Dynamic Contact Angle Analyzer and a KRUSSProcess Tensiometer K12, respectively. A Qualitest 1055 friction testerwas utilized to determine the kinetic coefficient of friction, and eachfilm was subjected to MEK double rubs to determine solvent resiliency.

EXAMPLE 2

FIGS. 1, A, B, and C illustrates transmission electron microscopy (TEM)micrographs of a series of p-MMA/nBA, P-MMA/nBA/FMA (FMA 8.5% w/w) andP-MMA/nBA/FMA (FMA 15% w/w) colloidal particles, respectively. As seen,p-MMA/nBA particles are spherical, whereas p-MMA/nBA/FMA exhibit morecomplex morphologies. As shown in FIG. 1, B, p-MMA/nBA/FMA particles8.5% w/w FMA) are non-spherical with the high electron density areas dueto p-FMA phase forming non-uniform shell around the p-MMA/nBA core. Asthe FMA content increases to 15% w/w, and DLPC phospholipids wasutilized, the size of p-FMA phase attached to the exterior of theparticles increase, giving multi-lobe morphologies. This is illustratedin FIG. 1, C.

The combination of DLPC with SDS/FSP surfactants results in thereduction of the overall surface tension of the aqueous phase from 72mN/m to about 1-5 mN/m. These conditions appear to be essential duringpolymerization of the F-containing colloidal particles because lowersurface tension facilitates not only efficient monomer transport to thepolymerization loci, but also provides stability of colloidal partiesafter synthesis.

As shown in Table 2, monodispersed particles are produced when DLPC andSDS/FSP surfactants are utilized. It is believed that this is attributedto similarities of head groups of DLPC and FSP and hydrophobic tails ofSDS and DLPC. When monomers diffuse through an aqueous phase to thenucleation site, the reduced surface tension and monomer starvationconditions facilitate transport of higher quantities and polymerizationof FMA into p-MMA/nBA particles. As MMA and nBA monomers initiallymigrate to the polymerization site, and upon initiation polymerize atthe reactive site, monomer starvation conditions force FMA to migrate tothe reactive site and diffuse to p-MMA/nBA copolymer core, which isfacilitated by the present of PL which lowers the surface tension suchthat colloidal particles containing hydrophobic-lipophobic entities ofp-FMA are stable and thus do not coagulate. Particle size measurementsduring polymerization indicate that the increase of the particle size issignificant at the initial states, whereas at later stages is muchslower. This behavior is attributed to faster MMA/nBA polymerization atthe early stages, followed by slower polymerization, which requiresmigration of FMA to the reactive site at the later stages. TABLE 2Composition and particle size analysis of colloidal dispersions (B) (C)(A) MMA/nBA/ MMA/nBA/ MMA/nBA FMA(8.5%) FMA(15%) FMA (% w/w) 0 3.3 5.8nBA (% w/w) 18.9 17.33 16.1 MMA (% w/w) 19.7 18.04 16.73 SDS (% w/w)0.91 0.91 0.91 FSP (% w/w) 0.58 0.58 0.58 DLPC (% w/w) 0.05 0.05 0.19KPS (% w/w) 0.23 0.23 0.23 DDI (% w/w) 59.5 59.5 59.5 Particle Size 110124 150 (nm) % Solids 40.5 40.5 40.5

The following materials, MMA, nBA, FMA, potassium persulfate (KPS), FSP,and SDS were purchased from Aldrich Chemical Co. DLPC phospholipids waspurchased from Avanti Polar Lipids, Inc. p-MMA/nBA/FMA emulsions weresynthesized using a semicontinuous process and adapted for small-scalepolymerization. The reaction flask was placed in a water bath set at 78°C. and purged using N₂ gas. The reaction flask was charged with 20 ml ofDDI water and while purging for 1 hour, the content was stirred at 300rpm. At this point all monomers and surfactants were dissolved in waterand stirred under high agitation to produce a semi-stable pre-emulsion.After which, 10% (w/w) of the pre-emulsion and 18% (w/w) of theinitiator solution was injected into the reaction kettle thusfacilitating the seeding of the emulsion polymerization. The remainingpre-emulsion was fed continuously over 4 hours while the initiatorsolution was fed over 4.5 hours. Upon the completion of initiator feed,polymerization was allowed to continue for another 4 hours. The amountof fluorine monomer incorporated into colloidal particles was determinedfrom the initial feed composition of the initiator monomer mixturecombined with the analysis of the solid content after the synthesis.Particle size measurements were obtained using a Microtrac UPA 250, andTable 2 lists the resulting particle sizes, % solids (% w/w) based onboth the initial feed as well as solid content analysis afterpolymerization, and concentration levels of individual components forp-MMA/nBA (A), p-MMA/nBA/FMA (8.5% w/w FMA) (B), and p-MMA/nBA/FMA (15%w/w FMA) (C). It should be noted that Table 2 lists the w/w% of eachcomposition utilized in the synthesis, and the % w/w of FMA listed aboverepresents the FMA content with respect to MMA and nBA monomers. Suchprepared colloidal dispersions were cast on a poly(vinyl chloride) PVC)substrate and allowed to coalescence at 50% relative humidity (RH) for 3days at 23° C. to form approximately 20 μm thick films.

EXAMPLE 3

This example focuses on the development of colloidal particlescontaining methyl methacrylate (MMA), n-butyl acrylate (nBA), and aseries of F-monomers. Specifically, the affect of the length of the CF₂tail on particle morphologies is studied as well as its effect on filmformation, structure-property relationships, and surface macroscopicproperties. For this experiment, we prepared methyl methacrylate/n-butylacrylate (MMA/nBA) colloidal dispersions in the presence of 8.5% (w/w)copolymer content of heptadecafluorodecyl methacrylate (FMA),heptadecafluorodecyl acrylate (FA), heptadecafluoro-1-decene (FD),heptafluorobutyl acrylate (FBA), and heptafluorobutyl methacrylate(FBMA).

Methyl methacrylate (MMA), n-butyl acrylate (nBA), heptadecafluorodecylmethacrylate (FMA), heptadecafluorodecyl acrylate (FA),heptadecafluoro-1-decene (FD), heptafluorobutyl acrylate (FBA),heptafluorobutyl methacrylate (FBMA), potassium persulfate (KPS),phosphoric acid bis(tridecafluoro-octyl) ester ammonium salt (FSP), andsodium dodecyl sulfate (SDS) were purchased from Aldrich Chemical Co.All colloidal dispersions were synthesized as described in Example 1.Such prepared colloidal dispersions were cast on a polyvinylchloride(PVC) substrate and allowed to coalescence at 50% relative humidity (RH)for 3 days at 23° C. to form approximately 20 μm thick dry films. Filmthickness was determined using a Pro Max caliper.

The synthesized colloidal particles consisted of MMA, nBA, and thefollowing F-containing monomers: FMA, FA, FD, FBMA, and FBA. Thecopolymer content of each F-containing monomer in the colloidalparticles was 8.5% (w/w). The amount of F-monomer incorporated intocolloidal particles was determined from the initial feed composition ofthe initial monomer mixture combined with the analysis of the solidcontent after synthesis.

Below are illustrated the structure of each F-containing monomer.

The particle size of each colloidal dispersion range from 94 to 105 nmwith mono-modal distribution of the particles regardless of theF-monomer utilized.

Transmission electron micrographs (TEM) were acquired on a Zeiss EM 109Tmicroscope using an accelerating voltage of 80 kV. Samples of colloidaldispersion used for TEM analysis were prepared by making a 1:10,000dilution in deionized water followed by casting onto Formvar coatedcopper grids (Ted Pella, Inc.).

In an effort to identify particle morphologies, TEM images werecollected of MMA/nBA (A), MMA/nBA/FMA (B), MMA/nBA/FA (C), MMA/nBA/FD(D), MMA/nBA/FBMA (E), and MMA/nBA/FBA (F). MMA/nBA colloidal particlesexist as mono-modal entities with no considerable electron densitychanges, indicating a random copolymerization process. On the otherhand, the presence of the long perfluoroalkyl side chains results inintra-particle phase separation with highly electron dense regionsexisting near the exterior of the particles. These data also show thatby decreasing the length of the perfluoroalkyl side chain, the size ofthe phase-separated entities within a particle decreases. These findingsconfirm that an appropriate FSP/SDS surfactant combination facilitatesthe copolymerization of MMA/nBA/F-containing colloidal particles, andthat F-monomer polymerizes as a blocky, phase-separated entity onto theexterior of existing p-MMA/nBA colloidal particles. The latter was alsoconfirmed by NMR measurements.

EXAMPLE 4

As stated in the Example 3, each colloidal dispersion is capable offorming a stable colloidal film, but the question is how the presence ofF-monomer copolymerized into MMA/nBA affects film properties as comparedto MMA/nBA. We utilized DMA to obtain the storage modulus attemperatures below the T_(g). The storage modulus of MMA/nBA is 615 MPa,whereas incorporation of 8.5% (w/w) FMA into MMA/nBA colloidal systemsresults in its increase to 850 MPa. This behavior is attributed to therigid nature of the F-containing monomer. Copolymerization of FA, FD,FBA, and FBMA into MMA/nBA colloidal particles also results in increasedstorage modules ranging from 720 to 900 MPa.

Thermal transitions were recorded using a TA Q800 dynamic mechanicalanalyzer (DMA) by heating the samples from −90° C. to 200° C. at a rateof 2° C./min and at a frequency of 1 Hz. Atomic force microscopy phaseimages (Nanoscope IIIa Dimension 3000 Scanning Probe Microscope, DigitalInstruments) were obtained using a Si cantilever at a resonancefrequency around 300 kHz.

With these data in mind, it is of interest to elucidate how thesedifferences affect surface macroscopic properties. For that purpose, wemeasured surface tension changes as well as the kinetic coefficients offriction at the F-A interface as a function of F-monomer, and theseresults are depicted in FIG. 2. Surface tension measurements ofpolymeric films were obtained using a FTA200 Dynamic Contact AngleAnalyzer, and a Qualitest 1055 friction tester was utilized to determinethe kinetic coefficient of friction.

As seen in FIG. 2, the presence of each copolymerized F-monomer altersthe contact angle of a drop of water at the surface for each film, whichfor MMA/nBA/FMA is 100° and for MMA/nBA, the contact angle is 69°.Similarly, MMA/nBA/FA and MMA/nBA/FD exhibit contact angles of 96 and101, respectively. However, the contact angle for the shorterperfluoroalkyl side chained MMA/nBA/FBMA and MMA/nBA/FBA colloidal filmsdecreases to about 90°. Although similar trends are observed for thekinetic coefficient of friction at the F-A interface, significantlylower values are observed for FMA, FA, and FD monomers. Similar to DMAexperiments, longer perfluoroalkyl side chains produce surfaces withmore polytetrafluoro ethylene-like properties.

At this point, it is clear that the length of the CF₂ side chains affectboth bulk and surface macroscopic measurements. The next question iswhat surface morphologies are responsible for these observeddifferences. FIG. 3 illustrates a series of AFM phase images recordedfrom the F-A interface for MMA/nBA (A), MMA/nBA/FMA (B), MMA/nBA/FA (C),MMA/nBA/FD (D), MMA/nBA/FBMA (E), and MMA/nBA/FBA (F). Each imagerepresents a 5×5 μm sample area. As shown, Image A displays a continuousone phase component attributed to p-MMA/nBA at the F-A interface,whereas Image B (MMA/nBA/FMA) indicates the presence of high aspectratio ordered entities at the F-A interface. Similar to previousstudies, the presence of the crystallites results from directionalstratification near the F-A interface. For comparison, Image C(MMA/nBA/FA) illustrates ordered domains of similar size and shape ofFMA at the F-A interface, thus indicating similar surface propertiesbetween the —CF₂)₇—CF₃ side chains of the acrylic and methacrylicF-monomers. On the other hand, the presence of the non-acrylic, vinylF-monomer with a similar —(CF₂)₇—CF₃ side chain results in surfacemorphologies with increased size of the crystalline or mesophase domainsat the F-A interface (Image D). Images E and F illustrate AFM images ofMMA/nBA/FBMA and MMA/nBA/FBA, respectively. As shown, there is asignificant decrease of the size and surface coverage of theheterogeneous domains as compared to Images B-D, which is attributed toboth FBMA and FBA possessing shorter perfluoroalkyl side chains(—(CF₂)₂—CF₃) subsequently leading to random aggregation with little tono crystalline components.

The chemicals disclosed herein are only representative of those suitablefor this application. One of ordinary skill in the art would readilyunderstand that a wide range of monomers can be polymerized, with one ormore being a fluoro-monomer, using a surfactant system comprised of afluoro-carbon containing phosphoric acid containing ester, anionic alkylsulfate, and a suitable biologically active phospholipid. The specificexamples listed herein are in no way meant to limit the scope of thisinvention.

REFERENCES

(1) Chen, Y.; Ying, L.; Yu, j. W.; Kang, E.; Neoh, K. Macromolecules2003, 36, 9451.

(2) Dargaville, T.; George, G.; Hill, D.; Whittacker, A. Macromolecules2004, 37, 360.

(3) Deng, T.; Ha, Y.; Cheng, J.; Ross, C.; Thomas, E. Langmuir 2002, 18,6719.

(4) Ding, L.; Olesik, S. Macromolecules 2003, 36, 4779.

(5) Fulton, J.; Deverman, G.; Yonker, C.; Grate, J.; De Yong, J.;McClain, J. Polymer 2004, 44, 3627.

(6) Gallyamoz, M.; Vinokur, R.; Nikitin, L.; Said-Galiyez, E.; Ernest,E.; Alexei, R.; Igor, V.; Schaumburg, K. Langmuir 2002, 18, 6928.

(7) Jin, J.; Smith, D.; Topping, C.; Suresh, S.; Chen, S.; Foulger, S.;Stephen, H.; Rice, N.; Nebo, J.; Mojazza, B. Macromolecules 2003, 36,9000.

(8) Kang, S.; Luo, J.; Ma, H.; Barto, R.; Frank, C.; Dalton, L.; Jen, A.Macromolecules 2003, 36, 4355.

(9) Prabhakar, R.; Freeman, B.; Roman, I. Macromolecules 2004, 37, 7688.

(10) Sung, L.; Vicini, S.; Ho, D.; Hedhli, L.; Olmstead, C.; Kurt, W.Polymer 2004, 45, 6639.

(11) Borkar, S.; Siesler, H.; Hvilsted, S. Macromolecules 2004, 37, 788.

(12) Parker, H.; Lau, W.; Rosenlind, E. S.; Rohm and Haas Co, Pat. No.6,218,464: USA, 2001.

(13) Banks, R. E.; Smart, B. E.; Tatlow, J. C. Organofluorine ChemistryPrinciples and Commercial Applications; Plenum Press: New York, 1994.

(14) Hiyama, T. Organofluorine Compounds; Springer-Verlag: Berlin, 2000.

(15) Lovell, P. A.; El-Aasser, M. S. Emulsion Polymerization andEmulsion Polymers; John Wiley & Sons: New York, 1997.

(16) LoNostro, P.; Choi, S.; Ku, C.; Chen, S. J. Phys. Chem. B 1999,103, 5347.

(17) Movchan, T.; Plotnikova, E.; Redina, L.; Gal'braikh, L.; Ys'yarov,O. Colloid Journal 2003, 65, 47.

(18) Ha, J.; Park, I.; Lee, S.; Kim, D. Macromolecules 2002, 35, 6811.

(19) Cheng, S.; Chen, Y.; Chen, Z. J. Appl. Polym. Sci. 2002, 85, 1147.

(20) Barthelemy, P.; tomao, V.; Selb, J.; Chaudeir, Y.; Pucci, B.Langmuir 2002, 18, 2557.

(21) Kuwarnura, S.; Hibi, T.; Agawa, T. In Waterborne & High-solids, andPowder Coatings Symopsium: New Orleans, La., 1997; p 406.

(22) Kostov, G.; Ameduri, B.; Boutevin, B. J. Fluor. Chem. 2002, 114,171.

(23) Huang, Z.; Shi, C.; Xu, J.; Kilic, S.; Enick, R.; Beckman, E.Macromolecules 2000, 33, 5437.

(24) Linemann, R. F.; Malner, T. E.; Brandsch, R.; Bar, G.; Ritter, W.;Mulhaupt, R. Macromolecules 1999, 32, 1715.

(25) Landfester, K.; Rothe, R.; Antonietti, M. Macromolecules 2002, 35,1658.

(26) Fasick, R.; Raynolds, S.; E.I. DuPont de Nemours and Co, Pat. No.3,282,905: USA, 1966.

(27) Fasick, R.; Johnson, R.; E.I. DuPont de Nemors Co, Pat. No.3,378,609: USA, 1968.

(28) Raynolds, S.; Tandy, T.; E.I. DuPont de Nemours Co, Pat. No.3,462,296, 1969.

(29) Kato, M.; Hiraharu, T.; Nishiwaki, K.; Tadenuma, H.; JapanSynthetic Rubber, Co., Pat. No. 5,349,003: USA, 1994.

(30) Kim, C. U.; Lee, J. M.; Ihm, S. K. J. Appl. Polym. Sci. 1999, 73,777.

(31) Tsuda, N.; Iwakiri, Y.; Imoto, K.; Shimizu, Y.; Araki, T.; Kondo,M.; Daiken Industries, Ltd., Pat. No. 5,804,650: USA, 1998.

(32) Yamana, M.; Uesugi, N.; Ogura, E.; Daikin Industries, Ltd, Pat. No.6,126,846: USA, 2000.

(33) Munekata, S. Prog in Org Coat 1988, 16, 113.

(34) Marion, P.; Beinert, G.; Juhue, D.; Lang, J. J. Appl. Polym. Sci.1997, 64, 2409.

(35) Marion, P.; Beinert, G.; Juhue, D.; Lang, J. Macromolecules 1997,30, 123.

(36) Thomas, R. R.; Lloyd, K. G.; Stika, L. M.; Stephans, L. E.;Magallanes, G. S.; Dimonie, V. L.; Sudol, E. D.; El-Aasser, M. S.Macromolecules 2000, 33, 8828.

(37) Adamson, A. W. Physical Chemistry of Surfaces, 2nd ed.; John Wiley& Sons, Inc., 1967.

(38) Wu, S. Polymer Interface and Adhesion; Marcel Dekker, Inc.: NewYork, 1982.

(39) Urban, M. W. Attenuated Total Reflectance Spectroscopy ofpolymersTheory and Practice; American Chemical Society, 1996.

(40) Urban, M. W. Encylcopedia ofAnalytical Chemistry; John Wiley &Sons, Ltd, 2000.

(41) Schaefer, J. S., E. O. Buchdahl, R. Macromolecules 1977, 10,384-405.

(42) 1894-01, A. S. D.

(43) 5402-93, A. S. D.

(44) Liu, S. F.; Schmidt-Rohr, K. Macromolecules 2001, 34, 8416.

(45) Urban, M. W.; Provder, T. Multidimensional Spectroscopy ofpolymers;American Chemical Society: Washington D.C., 1995.

(46) Odian, G. Principles of Polymerization, 3rd ed.; John Wiley & Sons,Inc.: New York, 1991.

(47) Brandrup, J.; Immergut, E. H. Polymer Handbook, 2 ed.; John Wiley &Sons, Inc: USA, 1975.

(48) Dreher, W. R.; Zhang, P.; Urban, M. W.; Porzio, R. S.; Zhao, C.Macromolecules 2003, 36, 1228.

(49) Eastoe, J.; Rankin, A.; Wat, R.; Bain, C.; Styrkas, D.; Penfold, J.Langmuir 2003, 19, 7734.

(50) Dreher, W. R.; Urban, M. Langmuir 2004, In Press.

(51) Shafrin, E.; Zisman, W. J. Phys. Chem. 1962, 66, 740.

1. A process for forming fluorine-containing water-dispersible latexescomprising: adding a fluoro-monomer and a co-monomer to a solutioncontaining a surfactant component comprising a fluorinated surfactant;and polymerizing the monomers.
 2. The process for formingfluorine-containing water-dispersible latexes as defined in claim 1wherein the co-monomer is an acrylate or methacrylate.
 3. The processfor forming fluorine-containing water-dispersible latexes as defined inclaim 1 wherein the co-monomer is n-butyl acrylate or methylmethacrylate.
 4. The process for forming fluorine-containingwater-dispersible latexes as defined in claim 1 wherein the co-monomercomprises n-butyl acrylate and methyl methacrylate.
 5. The process forforming fluorine-containing water-dispersible latexes as defined inclaim 1 wherein the fluoro-monomer is selected from the group consistingof heptadecafluorodecyl methacrylate, heptadecafluorodecyl acrylate,heptadecafluoro-1-decene, heptafluorobutyl acrylate and heptafluorobutylmethacrylate.
 6. The process for forming fluorine-containingwater-dispersible latexes as defined in claim 1 wherein the fluorinatedsurfactant is a fluorocarbon containing phosphoric acid ester salt. 7.The process for forming fluorine-containing water-dispersible latexes asdefined in claim 6 wherein the fluorinated surfactant is phosphoric acidbis(tridecafluoro-octyl) ester ammonium salt (FSP).
 8. The process forforming fluorine-containing water-dispersible latexes as defined inclaim 1 wherein the surfactant component further comprises an anionicsurfactant.
 9. The process for forming fluorine-containingwater-dispersible latexes as defined in claim 8 wherein the anionicsurfactant is sodium dodecyl sulfate.
 10. The process for formingfluorine-containing water-dispersible latexes as defined in claim 1wherein the surfactant component further comprises a phospholipiddispersing agent.
 11. A water dispersible colloidal particle comprisingtwo distinct polymeric phases, wherein polyacrylate or polymethacrylateform spherical particles and a non-spherical fluoro-polymer forms on theexterior of the spherical particles.
 12. The water dispersible colloidalparticle of claim 11, wherein the spherical particle comprises apolyacrylate/polymethacrylate co-polymer.
 13. The water dispersiblecolloidal particle of claim 11, wherein the non-spherical fluoro-polymeris formed from a fluoro-monomer selected from the group consisting ofheptadecafluorodecyl methacrylate, heptadecafluorodecyl acrylate,heptadecafluoro-1-decene, heptafluorobutyl acrylate and heptafluorobutylmethacrylate.
 14. The water dispersible colloidal particle of claim 11,wherein the fluoro-polymer comprises from 5 to 20% (w/w) of thecolloidal particle.
 15. A water dispersible colloidal particle formed bythe process of claim 1.